Heavy duty liquid detergent



United States Patent 1 2,914,482 HEAVY DUTY LIQUID DETERGENT MarvinKopp, Lenox, Mass., assignor to General Aniline & Film Corporation, NewYork, N. a corporation of Delaware No Drawing. Application June 11, 1956Serial No. 590,394 2 Claims. (Cl. 252-152) The invention here presentedis a new, heavy duty detergent, especially suitable for use in automaticwashing machines of the tumbling drum type, having a powerful detergentaction, suitable for use in relatively substanu'al quantities and at thesame time characterized by the production of a small amount of suds suchthat the amount is not sufiiciently great to overflow the washer whenenough is used to obtain the desired heavy duty detergent action; thedetergent of the invention being a combination of a nonionic surfactanttogether with ap propriate quantities of carboxymethyl cellulose and analkanolamine.

For laundering in the tumbling barrel type of washer, especially in thetumbling barrel automatic washers suitable for household use, it ishighly desirable that a high power detergent be used, and that it be ofsuch characteristics that it permits of the use of relatively largequantities of detergent. This requires, as a corollary, that the amountof suds produced be relatively small in order to avoid swamping of thedetergent efiect, and to prevent overflow of suds from the washer; andat the same time it is required that the detergent used shall have apowerful cleansing effect and a minimum tendency to redeposit dirt andsoil when it is once loosened from the fabrics being washed. To thepresent most detergents which are powerful enough for heavy duty serviceyield so much suds as to mutfle the detergent effect, and at the sametime to overflow a tumbling barrel type of washer, thereby hampering thedetergent effect or limiting the permissible amount used in any givenlaundering cycle to a quantity so low as to result in ineflicient orinadequate cleaning.

According to the present invention it is now found that a nonionicsurfactant may be mixed with carboxymethyl cellulose and an alkanolaminesuch as triethanolamine to produce a heavy duty, liquid detergent which,in action, produces a relatively small amount of suds, such that it maybe used in optimum concentration for maximum elficiency of launderingwithout filling the tumbling barrel and vat so full of suds as todetract from the laundering action, and withoutdanger of filling thewasher so full of suds as to cause overflow.

Thus, according to the present invention, there is provided a newcomposition of matter, characterized by a high power laundering actionwhile producing a relatively small amount of suds, in the form of amixture of a nonionic surfactant such as the compound resulting from areaction between a nonylphenol with from 4 to 30 molecules of ethyleneoxide in admixture with an appropriate amount of carboxymethyl celluloseand an alkanolamine such as triethanolamine. Other objects and detailsof the invention will be apparent from the following description. I

The primary component of the composition of matter of the presentinvention is a nonionic surfactant of the type disclosed in US.2,213,477 such as is produced by the reaction between ethylene oxide andan alkylphenol or an aliphatic hydroxy compound such as tridecyl alco-'hol, lauryl alcohol, etc. as shown in the following equations:

Q -(OHNEO) 1-H 2,914,482 Patented Nov. 24, 1959 (II) R-0-(cH,cH,0 ,H

in which x is preferably 10 but may vary between about 5 and 25, and Ris at least 12 carbon atoms, such as disclosed in US. 1,970,578. g

It will be observed that these compounds are nonionic and a majorportion of each is the polymerization product of ethylene oxide.

The second component of the composition of the invention iscarboxymethyl cellulose which is desirably present in the preparation ofA the amount of the nonionic surfactant but may vary in amount fromabout 5 to about A of the amount of the nonionic surfactant.

The third component of the composition of the invention then is analkanolamine, preferably triethanolamine which is desirably present inthe composition in an amount ranging from about /3 the amount of thesurfactant to an amount of approximately 1% times the amount of thesurfactant, preferably in an amount about equal to the amount ofsurfactants, these proportions being by weight. A considerable range ofalkanolamines may be used for this purpose and they may be either themono-, di-, or trilower alkanolamines, such as in which R is ahydroxyalkyl substituent and R and K may be hydrogen; alkyl orhydroxyalkyl and the total number of carbon atoms is not over about 13.Thus this component may be a monoethanolamine or may be adiethanolamine, or a triethanolamine, or may be a mono, di or triisopropanolamine, or may be monoethanolethylene diamine ormonoethanoldiethylenetriamine, or the analogous compounds having suchformulas as:

in which R and R have the same meanings as above and R is a short chainalkylene substituent.

The composition of matter of the invention is then prepared simply bymixing the three components with or without diluting water, and theresulting product is a clear, pourable, stable liquid suitable forpackaging or bottling and for shipment as desired. As so prepared, thecomposition of the invention may contain nonionic detergent, 10 parts toparts by weight carboxymethyl cellulose, 0.01 part to 10 parts by weightalkanolamine, 10 parts to 50 parts by weight.

In evaluating these mixtures, the procedure used was that shown byMayhew, Ielinek and Stefcik, as published in the July 1955 issue of theJournal of Soap and Chemical Specialties.

The following tests were made upon mixtures prepared as indicated aboveand they are offered as representative methods which are preferred forthe practice of the invention but are not intended to limit theinvention in any way.

In the table there are given 16 examples of specific detergentcompositions. Examples 1, 5, 6, 7, 8, 12, 13, 14 and 16 illustratecompositions embraced in the present invention. For comparisontherewith, there are given examples of compositions 2, 9 and 15 showingthe use of a nonionic surfactant without either triethanolamine orcarboxymethyl cellulose; Example 3 showing the efiect of water alone;Example 4 showing the composition con- I taining a water-insolublenonionic surfactant in combination with triethanolamine andcatboxymethyl celluloee; Example 10, a composition of a nonionicsurfactant and a triethanolamine but containing no carboxymethylcellulose; Example 11, a composition containing triethanolamine andcarboxymethyl cellulose but no nonionic surfactant. In Examples 1, 2, 3to 10 inclusive, 12, 13 and 16. the nonionic surfactant employed was analkylphenol condensed with ethylene oxide Le. a product of the ionicsurfactant used was the condensate of tridecyl alcohol with ethyleneoxide Le. a product of the formula R--O(CH,CH,O),H

which is identified by naming the alcohol employed and formula 10 theamount of ethylene oxide condensed therewith. In R the table the numberimmediately preceding ethylene (qmcmmrn oxide would be :c in theforegoing formulas. In the table tnethanolamine is sometimes abbreviatedas TEA and carboxymethyl cellulose is abbreviated as CMC.

flq-otometernetermey'ren: wetcflim'ltuiitatenpudmnpmeom product] Eltonhunter (Up.p.m.) Hard Water (500 p.p.m.)

Product ACE Test OEL Overall Bedepo- AOH M 08L Overall Bede cmn Fabric!rut Ave. lition 010th Fabrics Test Ave. sitlo #114 M Cloth Cloth 010thNonyl Phenol-H40 pts. 1 55.5 as ns 5 sas 52.0 an was 55.2 33.0

55.5 no as 52.8 53.5

[Maytag team and Detergeney Test (vacuum cleans dirt) with deloemeoil(cottonseed oil): Water 3 120 12:11.83); product] Elston Tepwuter (50p.p.m.) Herd Water (800 p.p.m.) 2mm,

Product ACE Test OBL OverellRedepo .AOH Test ORL OverallBedepo- 010thFabric: Test vs. m 010th Fabrics Cloth Ave. sitlon ETW p.p.m.

m4 no one: 010m 010th 5% igunyi ami-i-s-io pts. Ethyl a m m iiiifiii54.5 575 00.1 52.5 as 50.9 v55.0 50.2 51.0 s1.5 1.5 1.5

1;"; 9 i,:).* 4&5 40.5 55.5 51.5 no as 54.0 45.5 1.5 1.5

m0 p 3% NonylphemHO-IO Dts. Ethylin a 51 an 55.2 51.2 an 41.5 an as: as79.5 1.5 1.5

3&0 65.6

[Maytag Foam and Detergency Test (vacuum cleaner dirt) with defoam soil(cottonseed 011): Water 120 F.; 0.20% prodnct.]

Easton Tapwater (50 ppm.) Hard Water (300 ppm.) Foam Ht,

inches Product ACH Test GRL Overall Redepo- AOH Test CRL Overall Redepo-300 Cloth Fabrics giefi] Ave. sition Cloth Fabrics Cloth Ave. sition ETWp.p.m.

These results show a detergent efiiciency equal to or better than thebest commercial detergents, and in addition the products are clearsolutions when dissolved in water which do not separate on standing, arenot injured by cold, and yield a relatively small amount of suds, suchthat the detergent effect is not muffled by large quantities of suds,and there is no tendency of suds to overflow the tumbler barrel washingmachine.

It will be noted that all of the above formulae involve the use of analkanolamine such as triethanolamine. A substantial part of the presentinvention lies in thefact that the presence of the alkanolamine greatlyincreases the detergent properties of the nonionic surfactants.

Thus the composition of matter of the invention provides a new anduseful and highly eflicient detergent composition which will form aconcentrated aqueous so lution resistant to temperature changes, stableon storage and yielding a minor amount of suds while exerting a powerfuland potent detergent eifect in optimum concentration in wash water.

While there are above disclosed but a limited number of embodiments ofthe composition of matter of the invention it is possible to providestill other embodiments without departing from the inventive conceptherein disclosed, and it is therefore desired that only such limitationsbe imposed upon the appended claims as are stated therein or required bythe prior art.

The invention claimed is:

1. A heavy duty detergent composition consisting essentially of acombination of a water-soluble nonionic surface active agent of theformula wherein R represents a hydrocarbon radical selected from thegroup consisting of the hydrocarbon residue of tridecyl alcohol andnonylphenol and x represents an integer within the range of 9 to 30 withfrom A to ,6 by weight of said nonionic surface active agent ofcarboxymethyl cellulose and from /3 to 1 /2 times by weight of saidnonionic surface active agent of alkanol amine selected from the groupconsisting of mono, diand triethanol amine.

2. A heavy duty detergent composition consisting essentially of aboutequal parts by weight of triethanolamine and a nonionic surface activeagent of the formula n Hn together with about A the amount by weight ofsaid nonionic surface active agent of carboxymethyl cellulose.

References Cited in the file of this patent UNITED STATES PATENTS OTHERREFERENCES Condensed Chemical Dictionary, 4th Ed., pp. 229, 267, 268,371, 672, 673, pub. by Reinhold Pub. Corp., N.Y. (1950).

Sequestrene, p. 3, pub. by Geigy Ind. Chemicals, N.Y. (1952).

1. A HEAVY DUTY DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF ACOMBINATION OF A WATER-SOLUBLE NONIONIC SURFACE ACTIVE AGENT OF THEFORMULA